Basis Set Extrapolation of Vibrational Frequencies

Abstract

We investigate three different approaches for extrapolating harmonic vibrational frequencies to the complete basis set limit, by direct extrapolation of the frequencies, by calculation of frequencies based on extrapolated Hessians, or based on the Hessian from optimization of the extrapolated energy surface. For regular molecules, the three extrapolation procedures yield essentially identical results, but for loosely bound complexes, the frequencies derived from extrapolated Hessians yield unpredictable behavior. None of the basis set extrapolations, however, provide any significant improvement over the results upon which the extrapolation is based.